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Acta Cryst. (2007). E63, m1554    [ doi:10.1107/S1600536807020016 ]

Bis[(R)-1-phenylethylaminium] [mu]-oxalato-[kappa]4O,O':O''O'''-bis[diaqua(oxalato-[kappa]2O,O')cobaltate(II)]

X. Yang, J. Li, H.-W. Wang, X.-H. Zhao and Y.-K. Shan

Abstract top

The title compound, (C8H12N)2[Co2(C2O4)3(H2O)4], was prepared under hydrothermal conditions. The structure consists of chiral organic cations and complex anions. Hydrogen bonds and C-H...[pi](aryl) interactions give a herring-bone arrangement of the cations along the a axis.

Comment top

The crystal structure of the title compound, (I)(Fig. 1), consists of bicobalt oxalate complex anions [Co2(C2O4)3(H2O)4]2- and organic cations (C8H12N)+, joined into a two-dimensional sheet by hydrogen bonds. Owing to the presence of the chiral organic cation, the compound crystallizes in the polar space group C2. In the anion, there are two types of oxalates. One as tetradentate ligand bridges two Co atoms, each is coordinated by another type of oxalate as bidentate ligand in the same plane. Each Co atom is also bonded by two water molecules above and below the equatorial plane to produce a negative step-lamella. The bond angles around the Co atom range from 81.01 (9)° to 100.2 (2) °, and from 178.1 (2)° to 178.7 (2)°. The Co—O distances span from 2.062 (5)Å to 2.114 (3) Å. The organic cation contains a stereogenic center in its R configuration and has a normal structure similar to that described elsewhere (Shan & Huang, 2001). The cations are anchored in the pockets on the both faces of the puckered anionic lamella through hydrogen bonds with the distances ranging from 2.678 (8)Å to 2.976 (7)Å (Table 1), thus resulting in the formation of cation–anion–cation slab-sandwich layers with an arrangement of the cations held together by close C–H···π(aryl) interactions in a herring bone motif (Fig.2).

Related literature top

For related structure, see: Shan & Huang (2001).

Experimental top

Compound (I) was prepared by the hydrothermal reaction of Co(C2O4).2H2O(0.130 g, 0.71 mmol), (R)-(+)-1-phenylethylamine (0.062 g, 0.51 mmol) and water (0.6 ml) at 383 K for 3 d in a sealed thick-walled Pyrex tube. Light pink crystals of (I) were obtained in 40–50% yield.

Refinement top

H atoms on C and N atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å (aryl), 0.98Å (CH) and 0.96Å (CH3) and N—H = 0.89 Å and Uiso(H) = 1.2Ueq(C,N). H atoms on water molecules were located in a difference Fourier map and fixed with Uiso(H) = 1.2Ueq(O).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. [Symmetry code: (i) 1 - x, y, 1 - z.]
[Figure 2] Fig. 2. A packing diagram of (I), showing the cation–anion–cation slab-sandwich layers with a herring-bone arrangement of the cations.
(R)-1-Phenylethylaminium µ-oxalato-κ4O,O':O''O'''-bis[diaqua(oxalato-κ2O,O')cobalt(II)] top
Crystal data top
(C8H12N)2[Co2(C2O4)3(H2O)4]F(000) = 720
Mr = 698.36Dx = 1.639 Mg m−3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 4453 reflections
a = 10.973 (2) Åθ = 1.2–27.1°
b = 7.5560 (15) ŵ = 1.25 mm−1
c = 17.067 (3) ÅT = 296 K
β = 90.33 (3)°Plate, pink
V = 1415.0 (5) Å30.24 × 0.12 × 0.04 mm
Z = 2
Data collection top
Siemens Quantum CCD
diffractometer		1938 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
graphiteθmax = 25.5°, θmin = 1.2°
ω scansh = −13→10
3658 measured reflectionsk = −9→8
2268 independent reflectionsl = −20→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0589P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
2268 reflectionsΔρmax = 0.45 e Å−3
193 parametersΔρmin = −0.52 e Å−3
38 restraintsAbsolute structure: Flack (1983), 850 Fridel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.11 (3)
Crystal data top
(C8H12N)2[Co2(C2O4)3(H2O)4]V = 1415.0 (5) Å3
Mr = 698.36Z = 2
Monoclinic, C2Mo Kα radiation
a = 10.973 (2) ŵ = 1.25 mm−1
b = 7.5560 (15) ÅT = 296 K
c = 17.067 (3) Å0.24 × 0.12 × 0.04 mm
β = 90.33 (3)°
Data collection top
Siemens Quantum CCD
diffractometer		1938 reflections with I > 2σ(I)
3658 measured reflectionsRint = 0.020
2268 independent reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.102Δρmax = 0.45 e Å−3
S = 1.13Δρmin = −0.52 e Å−3
2268 reflectionsAbsolute structure: Flack (1983), 850 Fridel pairs
193 parametersFlack parameter: 0.11 (3)
38 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.29291 (4)0.98018 (18)0.41036 (3)0.02253 (17)
O10.4159 (6)0.8027 (5)0.4631 (3)0.0242 (13)
O20.4163 (5)1.1583 (6)0.4624 (3)0.0266 (13)
O30.1732 (5)1.1586 (6)0.3606 (3)0.0262 (14)
O40.1735 (6)0.8017 (6)0.3563 (3)0.0286 (15)
O5−0.0023 (6)0.8057 (7)0.2907 (3)0.0379 (16)
O6−0.0019 (5)1.1607 (6)0.2925 (3)0.0341 (15)
O70.3966 (2)0.9858 (9)0.30858 (15)0.0317 (6)
H7A0.44800.88820.29920.038*
H7B0.44911.07600.30100.038*
O80.1915 (2)0.9809 (10)0.51531 (15)0.0314 (6)
H8A0.14651.08920.52200.038*
H8B0.14870.87600.52440.038*
N10.2561 (3)0.4834 (10)0.28541 (18)0.0278 (7)
H1A0.33710.48220.28330.042*
H1B0.23060.39500.31560.042*
H1C0.23120.58600.30540.042*
C10.50000.8799 (16)0.50000.019 (2)
C20.50001.0861 (15)0.50000.021 (3)
C40.0833 (8)0.8815 (10)0.3241 (4)0.0194 (16)
C30.0844 (9)1.0873 (11)0.3269 (5)0.0275 (19)
C90.3493 (6)0.6631 (9)0.1348 (3)0.0599 (19)
H90.41340.59780.15600.072*
C80.3753 (9)0.8048 (11)0.0842 (4)0.081 (2)
H80.45530.83450.07220.098*
C70.2813 (10)0.8964 (11)0.0536 (5)0.086 (3)
H70.29750.98980.01980.103*
C60.1660 (9)0.8583 (11)0.0701 (4)0.083 (3)
H60.10330.92410.04770.100*
C50.1388 (7)0.7174 (10)0.1216 (4)0.067 (2)
H50.05820.69210.13370.080*
C100.2306 (8)0.6182 (9)0.1538 (4)0.0395 (18)
C110.2044 (4)0.4618 (12)0.2043 (2)0.0307 (12)
H110.11570.45170.20890.037*
C120.2513 (8)0.2897 (8)0.1688 (4)0.045 (2)
H12A0.21890.27630.11680.068*
H12B0.22580.19170.20050.068*
H12C0.33870.29280.16670.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0218 (3)0.0158 (3)0.0299 (3)−0.0009 (6)−0.00417 (19)0.0013 (6)
O10.034 (3)0.010 (3)0.029 (3)−0.001 (3)−0.008 (3)0.003 (2)
O20.018 (3)0.023 (3)0.039 (3)0.002 (3)−0.006 (2)0.005 (3)
O30.023 (3)0.018 (3)0.038 (3)−0.004 (2)−0.007 (3)0.002 (2)
O40.033 (4)0.016 (3)0.037 (3)−0.001 (3)−0.007 (3)−0.001 (2)
O50.038 (4)0.031 (4)0.044 (3)−0.004 (3)−0.020 (3)0.005 (3)
O60.032 (4)0.021 (3)0.050 (3)0.010 (3)−0.006 (3)0.000 (3)
O70.0339 (13)0.0203 (14)0.0412 (15)−0.001 (3)0.0077 (11)0.007 (3)
O80.0361 (13)0.0150 (12)0.0432 (15)−0.001 (3)0.0063 (11)−0.002 (3)
N10.0297 (15)0.0213 (15)0.0323 (16)−0.002 (4)0.0005 (13)0.003 (4)
C10.011 (5)0.029 (5)0.017 (4)0.000−0.001 (4)0.000
C20.030 (6)0.005 (4)0.029 (5)0.0000.004 (5)0.000
C40.014 (4)0.024 (4)0.019 (4)0.001 (3)−0.002 (3)0.000 (3)
C30.039 (5)0.015 (3)0.029 (4)0.004 (4)0.002 (4)−0.001 (3)
C90.073 (5)0.070 (5)0.037 (3)−0.032 (4)0.000 (3)0.005 (3)
C80.109 (6)0.082 (5)0.053 (4)−0.043 (5)0.008 (4)0.003 (4)
C70.149 (7)0.053 (4)0.056 (4)−0.010 (5)0.007 (5)−0.001 (3)
C60.132 (7)0.062 (4)0.056 (4)0.045 (5)−0.011 (5)0.010 (4)
C50.086 (5)0.064 (4)0.050 (4)0.038 (4)−0.003 (4)0.009 (4)
C100.055 (4)0.031 (4)0.033 (3)−0.003 (3)−0.007 (3)−0.008 (3)
C110.0267 (18)0.032 (4)0.034 (2)−0.005 (3)−0.0019 (16)0.001 (3)
C120.076 (5)0.027 (4)0.033 (4)0.002 (4)−0.003 (4)−0.010 (3)
Geometric parameters (Å, °) top
Co—O32.062 (5)C1—C21.558 (6)
Co—O72.083 (3)C2—O2i1.243 (7)
Co—O42.091 (5)C4—C31.556 (5)
Co—O12.102 (5)C9—C101.387 (10)
Co—O22.103 (6)C9—C81.406 (10)
Co—O82.114 (3)C9—H90.9300
O1—C11.257 (8)C8—C71.345 (12)
O2—C21.243 (7)C8—H80.9300
O3—C31.250 (10)C7—C61.329 (12)
O4—C41.281 (9)C7—H70.9300
O5—C41.237 (9)C6—C51.414 (11)
O6—C31.242 (10)C6—H60.9300
O7—H7A0.9420C5—C101.368 (10)
O7—H7B0.9020C5—H50.9300
O8—H8A0.9630C10—C111.491 (11)
O8—H8B0.9349C11—C121.525 (11)
N1—C111.503 (5)C11—H110.9800
N1—H1A0.8900C12—H12A0.9600
N1—H1B0.8900C12—H12B0.9600
N1—H1C0.8900C12—H12C0.9600
C1—O1i1.257 (8)
O3—Co—O789.6 (2)O5—C4—O4124.3 (8)
O3—Co—O481.01 (9)O5—C4—C3118.9 (9)
O7—Co—O489.4 (2)O4—C4—C3116.8 (9)
O3—Co—O1178.7 (2)O6—C3—O3128.0 (8)
O7—Co—O191.0 (2)O6—C3—C4115.2 (9)
O4—Co—O1100.2 (2)O3—C3—C4116.8 (9)
O3—Co—O299.4 (2)C10—C9—C8121.6 (8)
O7—Co—O289.2 (2)C10—C9—H9119.2
O4—Co—O2178.5 (3)C8—C9—H9119.2
O1—Co—O279.45 (9)C7—C8—C9118.2 (8)
O3—Co—O890.6 (2)C7—C8—H8120.9
O7—Co—O8178.1 (2)C9—C8—H8120.9
O4—Co—O892.5 (2)C6—C7—C8122.4 (8)
O1—Co—O888.7 (2)C6—C7—H7118.8
O2—Co—O888.9 (2)C8—C7—H7118.8
C1—O1—Co112.7 (6)C7—C6—C5119.9 (8)
C2—O2—Co114.2 (6)C7—C6—H6120.0
C3—O3—Co113.6 (5)C5—C6—H6120.0
C4—O4—Co111.5 (5)C10—C5—C6120.4 (8)
Co—O7—H7A117.1C10—C5—H5119.8
Co—O7—H7B119.1C6—C5—H5119.8
H7A—O7—H7B100.6C5—C10—C9117.5 (7)
Co—O8—H8A112.0C5—C10—C11121.5 (7)
Co—O8—H8B113.9C9—C10—C11120.9 (7)
H8A—O8—H8B116.2C10—C11—N1111.9 (6)
C11—N1—H1A109.5C10—C11—C12112.3 (4)
C11—N1—H1B109.5N1—C11—C12109.4 (6)
H1A—N1—H1B109.5C10—C11—H11107.7
C11—N1—H1C109.5N1—C11—H11107.7
H1A—N1—H1C109.5C12—C11—H11107.7
H1B—N1—H1C109.5C11—C12—H12A109.5
O1—C1—O1i124.7 (12)C11—C12—H12B109.5
O1—C1—C2117.6 (6)H12A—C12—H12B109.5
O1i—C1—C2117.6 (6)C11—C12—H12C109.5
O2i—C2—O2128.0 (12)H12A—C12—H12C109.5
O2i—C2—C1116.0 (6)H12B—C12—H12C109.5
O2—C2—C1116.0 (6)
Symmetry codes: (i) −x+1, y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O40.891.952.843 (8)176
N1—H1B···O3ii0.892.052.918 (8)166
N1—H1A···O6iii0.892.232.976 (7)141
N1—H1A···O5iii0.892.212.973 (7)143
O8—H8B···O2iv0.931.812.737 (9)172
O8—H8A···O1v0.961.772.728 (9)172
O7—H7B···O5vi0.901.822.678 (8)157
O7—H7A···O6iii0.941.812.712 (8)159
Symmetry codes: (ii) x, y−1, z; (iii) x+1/2, y−1/2, z; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y+1/2, −z+1; (vi) x+1/2, y+1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O40.891.952.843 (8)176
N1—H1B···O3i0.892.052.918 (8)166
N1—H1A···O6ii0.892.232.976 (7)141
N1—H1A···O5ii0.892.212.973 (7)143
O8—H8B···O2iii0.931.812.737 (9)172
O8—H8A···O1iv0.961.772.728 (9)172
O7—H7B···O5v0.901.822.678 (8)157
O7—H7A···O6ii0.941.812.712 (8)159
Symmetry codes: (i) x, y−1, z; (ii) x+1/2, y−1/2, z; (iii) −x+1/2, y−1/2, −z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x+1/2, y+1/2, z.
Acknowledgements top

We thank the National Natural Science Foundation of China (Grants No. 20273021) and Key Project of Shanghai Science and Technology Committee (Nos. 05JC14070, 06DZ05025) for financial support.

references
References top

Bruker (2001). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Shan, Y. K. & Huang, S. P. (2001). Z. Kristallogr. 216, 373–374.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GöEttingen, Germany.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.